CN105829556A - Copper alloy sheet material, connector, and production method for copper alloy sheet material - Google Patents

Copper alloy sheet material, connector, and production method for copper alloy sheet material Download PDF

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Publication number
CN105829556A
CN105829556A CN201480070508.7A CN201480070508A CN105829556A CN 105829556 A CN105829556 A CN 105829556A CN 201480070508 A CN201480070508 A CN 201480070508A CN 105829556 A CN105829556 A CN 105829556A
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mass
copper alloy
orientated
alloy plate
orientation
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CN201480070508.7A
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CN105829556B (en
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金子洋
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Abstract

Provided is a copper alloy sheet material which is suited for use in a connector or the like, and which simultaneously exhibits a high yield strength, good bending workability and good electrical conductivity. Specifically provided is a copper alloy sheet material having a composition that contains a total of 1.80-8.00 mass% of one or more of Ni and Co, 0.40-2.00 mass% of Si, and a total of 0.000-2.000 mass% of at least one element selected from the group consisting of Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti, with the remainder being copper and inevitable impurities, wherein the orientation density of the {121}<111> component is 6 or less, the orientation density of the {110}<001> component is 4 or greater, and the concentration of crystal grains having the {110}<001> component is 0.40 crystals/[mu]m2. Also provided are a connector using the copper alloy sheet material, and a production method for the copper alloy sheet material.

Description

The manufacture method of copper alloy plate, adapter and copper alloy plate
Technical field
The present invention relates to copper alloy plate and employ the adapter of this copper alloy plate and the manufacture method of this copper alloy plate.
Background technology
Along with the miniaturization of the miniaturization of electric/electronic in recent years, terminal and contact component is carried out.Such as in electric contact, if the size constituting the parts of spring diminishes, its length shortens, and the bearing strength test hence for spring copper alloy raises.When this stress is higher than the yield point of Cu alloy material, material generation permanent deformation, desired contact pressure cannot be obtained as spring.In the case of Gai, contact resistance rises, and electrical connection becomes insufficient, can become serious problem.It is therefore desirable to copper alloy has high intensity.
It addition, generally curved processability and intensity have the relation of balance.Additionally, along with the miniaturization of electric/electronic, putting on the bending radius in the bending machining of material needs to diminish.Due to the technology trend of this electronic equipment, need the material that high intensity and bendability are also excellent.
Additionally, by making terminal miniaturization one by one, the sectional area of energising reduces, it is impossible to the desired electric current that circulates becomes problem.Such as, as terminal material, phosphor bronze can be enumerated as general copper alloy, if but the one-tenth of high intensity be grouped into, electrical conductivity is about 10%IACS, insufficient for small-sized terminal.If it addition, electronics miniaturization, then thermal capacity reduces, if thus the Joule heat of conductor becomes big, then be directly connected to equipment overall temperature rise, problem can be become.It is therefore desirable to copper alloy has good electric conductivity.
But, above-mentioned high intensity (such as high-yield strength) and good electric conductivity are contrary characteristic for copper alloy.To this, high intensity to be realized and the trial of good electric conductivity had been carried out with each Albatra metal in the past.
Patent documentation 1 proposes following proposal: the alloy containing composition comprising Cu-Ni-Sn system alloy by selection forms, specific operation carries out Precipitation hardening, thus the copper alloy that high intensity, fatigue properties are good can be formed.
Patent documentation 2 proposes following proposal: adjust crystallization particle diameter and the finish rolling condition of Cu-Sn system alloy, thus make the copper alloy of high intensity.
Patent documentation 3 proposes following proposal: in Cu-Ni-Si alloy in the case of Ni concentration height, by being prepared in specific operation, high intensity can be formed.
Patent documentation 4 proposes following proposal: the alloy containing composition comprising Cu-Ti system alloy by selection forms, and carries out Precipitation hardening, thus can form high intensity in specific operation.
Patent documentation 5 proposes following proposal: by obtaining Cu-(Ni, Co)-Si system sheet alloy in specific manufacturing process, the area occupation ratio in (100) face towards RD can be improved, reduction, towards the area occupation ratio in (111) face of RD, reaches the low Young's modulus of below 110GPa in rolling direction (RD).
Patent documentation 6 proposes following proposal: by obtaining Cu-Ni-Si alloy bar in specific manufacturing process, there is { the 110}<001>orientation density and KAM (KarnelAverageMisorientation of regulation, Karnel average orientation is poor) value, can improve deep drawability and fatigue-resistance characteristics.
Patent documentation 7 proposes following proposal: by obtaining Cu-Ni-Si alloy bar in specific manufacturing process, gathering in (220) face can be improved, the X-ray diffraction intensity with regulation high for I (220) and the particle diameter of the relation at plate width direction and thickness of slab direction with regulation, improve the bendability in the GoodWay bending making bending axis and rolling direction at a right angle.
Patent documentation 8 proposes following proposal: by obtaining Cu-Ni-Si alloy plate in specific manufacturing process, thus for the 001}<100>texture that ratio is more than 50% that is orientated, and not there is laminar boundary, intensity is high, can improve bendability.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-312937 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-294367 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-152392 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-132594 publication
Patent documentation 5: International Publication WO2011/068134A1
Patent documentation 6: Japanese Unexamined Patent Publication 2012-122114 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2006-9108 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2006-152392 publication
Summary of the invention
The problem that invention is to be solved
But, in patent documentation 1～4, although obtained high intensity compared with general copper alloy, but due to alloy system and the difference of manufacture method, electrical conductivity is the lowest sometimes.It addition, bendability is the most insufficient.It addition, in patent documentation 5～8, although obtain high conductivity and good bendability, but from the standpoint of yield strength, there is also the leeway of raising.
There is good electric conductivity accordingly, it would be desirable to a kind of and there is high-yield strength and there is the copper alloy plate of good bendability.
In view of above-mentioned problem, the problem of the present invention is to provide a kind of copper alloy plate, employ the adapter of this copper alloy plate and the manufacture method of this copper alloy plate, and this copper alloy plate has taken into account high-yield strength, good bendability, good electrical conductivity.Particularly, the problem of the present invention is to provide the copper alloy plate of adapter and the terminal material etc. that are suitable for the automobile mounted use such as the relay of electric/electronic, switch, socket etc.；And it is suitable in the electronic equipment parts such as auto-focusing camera module the copper alloy plate of the adapter etc. of electric conductivity spring material used or FPC (FlexiblePrintedCircuit, flexible printed circuit)；Employ the adapter of this copper alloy plate；Manufacture method with this copper alloy plate.
For solving the scheme of problem
The present inventor has carried out in-depth study repeatedly to solve above-mentioned problem, found that, by suppression 121}<111>and be orientated gather and improve at { 110}<001>gathering of being orientated, make that { 110}<001>crystal grain that is orientated disperses to high-density simultaneously, thus while there is good electric conductivity, it is possible to take into account high intensity and good bendability.In more detail, find while there is good electric conductivity, maintain and the most equal bendability, and intensity can be improved.Based on this technological thought, complete the present invention.
That is, according to the present invention, it is possible to provide following technical proposals.
(1) a kind of copper alloy plate, it is characterized in that, it has a following composition: containing any a kind or 2 kinds and 0.40 mass % in Ni and Co adding up to 1.80 mass %～8.00 mass %～the Si of 2.00 mass %, and remaining part is made up of copper and inevitable impurity
121}<111>the orientation density that is orientated is less than 6,110}<001>the orientation density that is orientated is more than 4,
Have that { 110}<001>density of crystal grain that is orientated is 0.40/μm2Above.
(2) a kind of copper alloy plate, it is characterized in that, it has following composition: containing any a kind or 2 kinds in Ni and Co adding up to 1.80 mass %～8.00 mass %, 0.40 mass %～the Si of 2.00 mass %, and the free Sn of choosing adding up to 0.000 mass %～2.000 mass %, Zn, Ag, Mn, P, Mg, Cr, Zr, at least one element in the group of Fe and Ti composition, and remaining part is made up of copper and inevitable impurity, { 121}<111>the orientation density that is orientated is less than 6, { 110}<001>the orientation density that is orientated is more than 4, have that { 110}<001>density of crystal grain that is orientated is 0.40/μm2Above.
(3) copper alloy plate as described in (2) item, it contains at least one element in the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition adding up to 0.005 mass %～2.000 mass %.
(4) copper alloy plate as according to any one of (1)～(3), its Vickers hardness is more than 280.
(5) a kind of adapter, its copper alloy plate comprised according to any one of (1)～(4) forms.
(6) manufacture method of a kind of copper alloy plate, it is characterized in that, this manufacture method carries out following operation successively: melt-casting operation, wherein, to there is the melting sources of following composition and cast, this consists of: containing any a kind or 2 kinds and 0.40 mass % added up in Ni and Co of 1.80 mass %～8.00 mass %～the Si of 2.00 mass %, and remaining part is made up of copper and inevitable impurity；Working modulus is the middle cold rolling process of 20%～70%；Ageing treatment process, wherein, carries out 5 minutes～10 hours heat treatments at 300 DEG C～440 DEG C；With the final cold rolling process that working modulus is more than 90%.
(7) manufacture method of a kind of copper alloy plate, it is characterized in that, this manufacture method carries out following operation successively: melt-casting operation, wherein, to there is the melting sources of following composition and cast, this consists of: containing any a kind or 2 kinds in Ni and Co adding up to 1.80 mass %～8.00 mass %, 0.40 mass %～the Si of 2.00 mass %, and the free Sn of choosing adding up to 0.000 mass %～2.000 mass %, Zn, Ag, Mn, P, Mg, Cr, Zr, at least one element in the group of Fe and Ti composition, and remaining part is made up of copper and inevitable impurity；Working modulus is the middle cold rolling process of 20%～70%；Ageing treatment process, wherein, carries out 5 minutes～10 hours heat treatments at 300 DEG C～440 DEG C；With the final cold rolling process that working modulus is more than 90%.
(8) manufacture method of the copper alloy plate as described in (7) item, it contains at least one element in the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition adding up to 0.005 mass %～2.000 mass %.
(9) manufacture method of the copper alloy plate as according to any one of (6)～(8), wherein, between above-mentioned melt-casting operation and above-mentioned middle cold rolling process, carry out following operation successively: homogenize heat treatment step, wherein, the heat treatment of more than 1 hour is carried out at 960 DEG C～1040 DEG C；With from hot-working start to the temperature range terminated be 500 DEG C～1040 DEG C, working modulus be the hot procedure of 10%～90%, the operation after above-mentioned hot-working does not carry out the heat treatment of more than 480 DEG C.
(10) manufacture method of the copper alloy plate as according to any one of (6)～(9), wherein, carries out keeping 5 seconds～the stress relief annealing of 2 hours at 200 DEG C～430 DEG C after above-mentioned final cold rolling process.
The effect of invention
The copper alloy plate of the present invention has has taken into account high-yield strength, good bendability, the characteristic of good electrical conductivity.
Therefore, can be suitable for the relay of electric/electronic, switch, socket etc. automobile mounted with etc. adapter and the electronic equipment part such as terminal material etc. and auto-focusing camera module in electric conductivity spring material used or the adapter etc. of FPC (FlexiblePrintedCircuit, flexible printed circuit).
It addition, the copper alloy plate of the present invention has and has high-yield strength while the most equal bendability, therefore can serve as the materials for springs that elastic force is difficult to weaken.It is thus possible, for instance be suitable as connector material.
It addition, the manufacture method of the copper alloy plate according to the present invention, can suitably manufacture the copper alloy plate with above-mentioned excellent specific property.
Accompanying drawing explanation
Fig. 1 is to illustrate { the schematic diagram in the direction of the 121}<111>structure cell of 2 variants that is orientated and copper alloy crystallization.
Fig. 2 is to illustrate { the schematic diagram in the direction of the 110}<001>structure cell that is orientated and copper alloy crystallization.
Fig. 3 is to illustrate { the schematic diagram in the direction of the 001}<100>structure cell that is orientated and copper alloy crystallization.
Fig. 4 is the crystal boundary figure (with a portion of amplification to measuring the visual field) obtained by FE-SEM/EBSD mensuration of example 204.In figure, only { 110}<001>orientation crystal grain white illustrates.
Fig. 5 is the crystal boundary figure (with a portion of amplification to measuring the visual field) obtained by FE-SEM/EBSD mensuration of comparative example 252.In the same manner as Fig. 4, the most only { 110}<001>orientation crystal grain white illustrates.
Detailed description of the invention
The preferred implementation of the copper alloy plate of the present invention is described in detail.Herein, " Cu alloy material " refers to that copper alloy raw material is processed to the material of regulation shape (such as plate, bar, paper tinsel, rod, line etc.).Wherein, sheet material refers to have specific thickness, dimensionally stable, the material that extends at in-plane, broadly includes web, foil, plate is made the tubing of tubulose.
Known: Cu-(Ni, Co)-Si system used in the copper alloy plate of the present invention is precipitation hardening type alloy, the compounds such as Ni-Si system, Co-Si system, Ni-Co-Si system as second with the size dispersion of about 10nm in Copper substrate, thus available high intensity.But, in the strengthening mechanism relying on this precipitation strength, may not balancedly take into account intensity and the bendability being in trade-off relationship, thus different strengthening mechanisms is studied by the present inventor.Results verification arrives, and by suitably controlling aggregation degree and both uniformities of microscopic scale of the macroscopic view of crystal orientation, can meet the characteristic of these balances, this completes the present invention.
Generally, having 12 slip systems in the face-centered cubic crystalline substance metal such as copper, (111) face of crystallization, along<011>direction sliding deformation, forms the plastic strain of macroscopic view by the shear strain of its pettiness.The curved outside of the material in flexural deformation, is extended by bending direction, shrinks in thickness of slab direction, fetters in the essentially a zero so-called plasticity of width strain, thus the most movable slip system minimizing.Its result, in the case of the plastic deformation difficulty that crystallization sliding causes, forms local deformation band or shear band as secondary deformation mechanism, assume responsibility for most plastic strain.Further, deformation concentrates on these local, can crack along these regions.About { 121}<111>orientation, owing to the geometry of slip system configures, needs substantial amounts of sliding deformation, thus easily produce the local deformations such as shear band, and result easily cracks.On the other hand, about { 110}<001>orientation, owing to the geometry of slip system configures, can be effectively formed the plastic strain of macroscopic view by less sliding deformation.Accordingly, it is difficult to produce the local deformations such as shear band, it is suppressed that crackle.Thus, reduce 121}<111>it is orientated, increases that { 110}<001>orientation is effective for preventing the crackle in flexural deformation.
(the orientation density analyzed based on ODF)
The analysis of orientation density includes (1) method based on X-ray pole graph and (2) method based on FE-SEM/EBSD method both.It should be noted that FE-SEM/EBSD refers to the abbreviation of FieldEmissionElectronGun-typeScanningElectronMicroscope/ ElectronBackscatterDiffraction (field emission gun, scanning electron microscope/EBSD).
(1) method based on X-ray pole graph
From plate surface measurements { 111}, { 100}, { the incomplete pole graph of 110}.With measure face specimen size as 25mm × 25mm is measured.About specimen size, if making the beam diameter of X-ray attenuate, then specimen size can be reduced.Based on 3 pole graphs measured, carry out ODF (OrintatiaonDistributionFunction: orientation density fonction) and analyze.Orientation density refers to, the state of random crystal orientation distribution is set to 1, and orientation density represents and reached several times gather relative to this, is common as crystal orientation distribution carries out the method for quantitative assessment.The symmetry of sample is orthotropic (Orthotropic) (being that minute surface is symmetrical at RD and TD), and launching number of times is 22 times.Further, { 121}<111>orientation, { 110}<001>orientation and { 001}<100>the orientation density that is orientated are obtained.
As shown in Figure 1, Figure 2 and Figure 3, due to the symmetry of crystallization, { 121}<111>variant that is orientated is 2, and { 110}<001>variant that is orientated is 1, and { 001}<100>variant that is orientated is 1.Orientation density in the present invention is defined by the orientation density of 1 variant.It should be noted that, record about orientation, use with the rolling direction (RD) of material as X-axis, with plate width direction (TD) as Y-axis, to roll the normal direction (ND) rectangular coordinate system as Z axis, each region in the material, use index (hkl) and the index [uvw] of (with rolling surface vertical) crystallization direction parallel with X-axis of (with rolling surface parallel) crystal face vertical with Z axis, represent with the form of (hkl) [uvw].In the case of representing single crystal orientation, it is expressed as (hkl) [uvw], in the case of representing the orientation entirety of equivalence on the basis of symmetry, changes the kind of bracket and be expressed as { hkl}<uvw>.
(2) method based on FE-SEM/EBSD method
ODF can also be obtained by crystal orientation measure of spread based on EBSD method.In particular it is preferred that use the FE-SEM/EBSD method that diameter is thin, position resolution is high of electron ray.In the case of EBSD method, Kikuchi style obtain crystal orientation, but in the case of the deformation of lattice is big, Kikuchi style becomes the distinctest, it is impossible to the point of analysis increases.If less than about 2 one-tenth of this point that cannot analyze all measuring points, then obtaining the measurement result equal with the analysis result of the texture utilizing X-ray pole graph to obtain.But, measure in the mensuration of EBSD method the visual field narrow in the case of, as { 121}<111>(121) [1-11] orientation of 2 variants of being orientated and (121) [-11-1] orientation density of being orientated are the most different.In the case of Gai, need to increase the quantity in the visual field, so that the orientation density of the orientation variant of these equivalences is equal.
In the present invention, by utilize that said method evaluates 121}<111>the orientation density contact that is orientated be less than 6 and by the case of 110}<001>the orientation density that is orientated brings up to more than 4, available good characteristic.{ 121}<111>the orientation density that is orientated is more preferably less than 4, more preferably less than 2.It addition, { 110}<001>the orientation density that is orientated is more preferably more than 7, more preferably more than 9.In the present invention, more preferably { 121}<111>the orientation density that is orientated is less than 4 and { 110}<001>the orientation density that is orientated is more than 7, and further preferably { 121}<111>the orientation density that is orientated is less than 2 and { 110}<001>the orientation density that is orientated is more than 9.To the 110}<001>higher limit of orientation density that is orientated is not particularly limited, and usually less than 100.
It addition, { 001}<100>the orientation density that is orientated is preferably less than 3.{ 001}<100>the orientation density that is orientated is more preferably less than 2, more preferably less than 1.{ 001}<100>the orientation density that is orientated is particularly preferably 0, is the most particularly preferably completely absent { 001}<100>orientation crystal grain.This is because, if { 001}<100>the orientation density that is orientated is too high, reduces yield strength sometimes.
As long as it should be noted that do not carry out the special rollings such as unlubricated rolling, warm-rolling, unsymmetrical rolling, then defining same tissue in thickness of slab direction, thus, the position in the thickness of slab direction evaluating crystal orientation distribution is not limited to surface.
In the present invention, X-ray pole graph uses " X ' PertPRO " that PANalytical society manufactures in measuring, use the analysis software " StandardODF " of Co., Ltd.'s Norm engineering during additionally ODF analyzes.
Additionally, during EBSD measures, the FE-SEM of electronic radial source uses " JSM-7001F " of Jeol Ltd., the photographing unit of analyzing of the Kikuchi pattern that EBSD analyzes uses " OIM5.0HIKARI " of Co., Ltd. TSL.
Additionally, the software " OIMAnalysis5 " analyzing use TSL society of EBSD data.
In the present invention, crystal orientation distribution function (ODF) utilizes Series Expansion Method, obtains by also introducing the calculating of odd term.The computational methods of odd term are such as such as metal (light metal), aboveground rich history work, " set three-D orientation resolves (the 3 D tropism analysis of texture) ", page 358～367 (1992)；Japan's metallography can will, aboveground rich Shi Dengzhu, " anti-number exhibition method To I Ru not exclusively puts か ら chip position distribution number fixed (being determined crystal orientation distribution function by incomplete pole graph based on iteration Series Expansion Method) ", page 892～898, volume 58 (1994)；U.F.Kocks et al.., " TextureandAnisotropy (tissue and anisotropy) ", page 102～125, described in CambridgeUniversityPress (Cambridge University Press) (1998) as.
(110}<001>density of crystal grain that is orientated)
As it has been described above, the 110}<001>crystal grain that is orientated has a flourishing effect weakening shear band, thus the 110}<001>crystal grain that is orientated disperses densely, thus can prevent crackle in flexural deformation, therefore preferably.It addition, { 110}<001>crystal grain that is orientated and grain formation wide-angle grain circle for other surroundings being orientated.This crystal boundary becomes the resistance of indexing motion, therefore acts on high intensity.Wherein, if { 110}<001>crystal grain that is orientated is the finest, then be difficult to give play to the effect preventing crackle, so this crystal grain preferably has has the dimensions (more than major diameter 0.2 μm).About 110}<001>be orientated the density of crystal grain seek method, first, utilize above-mentioned FE-SEM/EBSD method to carry out the scanning of electron ray with 0.05 μm interval, measure crystal orientation figure, extract out with ideal orientation the 110}<001>deviation angle that is orientated be ± 20 ° within crystal grain data.Further, the number of the crystal grain that major diameter is more than 0.2 μm is therefrom obtained.Further, by this number divided by all measuring area, as every 1 μm2There is { 110}<001>the density of crystal grain that is orientated.In this specification, { 110}<001>crystal grain that is orientated also referred to as { 110}<001>crystal grain that is orientated or { 110}<001>orientation crystal grain by having.
In the present invention, { 110}<001>orientation crystal grain so and the grain formation high-angle boundary of surrounding, thus carry out high intensity, and by the effect to above-mentioned resistance to crackle, can take into account in two kinds of characteristics and also have while the most equal bendability with high-yield strength.Required condition is taken into account, it is believed that { entire amount of 110}<001>orientation crystal grain is many, and is not sporadically to exist, but certain size disperses uniformly above as this.
In the copper alloy plate of the present invention, need with 0.40/μm2Above high density is dispersed with and has { 110}<001>the crystal grain that is orientated.Have that { 110}<001>density of crystal grain that is orientated is more preferably 0.55/μm2Above, more preferably 0.70/μm2Above.{ 110}<001>higher limit of the density of crystal grain that is orientated is not particularly limited, usually 20/μm to having2Below.It should be noted that the analysis of above-mentioned crystal grain can also be carried out based on the observed result obtained by transmission electron microscope.
(alloy composition)
·Ni、Co、Si
For constituting the element of above-mentioned second phase.They form above-mentioned intermetallic compound.They are the necessary addition element of the present invention.The summation of the content of any a kind or 2 kinds in Ni and Co is 1.8 mass %～8.0 mass %, is preferably 2.6 mass %～6.5 mass %, more preferably 3.4 mass %～5.0 mass %.It addition, the content of Si is 0.4 mass %～2.0 mass %, is preferably 0.5 mass %～1.6 mass %, more preferably 0.7 mass %～1.2 mass %.In the case of the addition of these necessary addition element is very few, obtained effect is insufficient, addition too much in the case of, rolling process produces material crack sometimes.During it should be noted that add Co, electric conductivity is the best, but when comprising Co in the case of the concentration height of these necessary addition element, according to hot rolling and the difference of cold rolling condition, is sometimes prone to produce rolling crack.Thus, as the preferred mode in the present invention, without Co.
Other elements
In addition to above-mentioned necessary addition element, the copper alloy plate of the present invention can also be containing at least one element optionally addition element in the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition.The following effects of these elements is confirmed: can be by { 121}<111>the orientation density domination that is orientated is relatively low, { 110}<001>the orientation density that is orientated can be improved, can improve simultaneously and have that { 110}<001>density of crystal grain that is orientated, optimizes Vickers hardness (Hv).In the case of containing these elements, the content of at least one element in the group that free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti form is selected preferably to add up to 0.005 mass %～2.0 mass %.But, if the content of these optional addition element is too much, produces the most sometimes and reduce the baneful influence of electrical conductivity or in rolling process, produce material crack sometimes.
Inevitably impurity
Inevitable impurity in copper alloy is the common element comprised in copper alloy.As inevitable impurity, such as, can enumerate O, H, S, Pb, As, Cd, Sb etc..They allow to contain below about 0.1 mass % with the gauge added up to.
(manufacture method)
As existing method, in the manufacture method of common precipitation hardening type copper alloy material, after forming super saturated solid solution state by solution heat treatment, make it separate out by Ageing Treatment, and carry out skin-pass (finish rolling) and quenched annealing (process annealing, strain annealing) as required.Manufacture method J of aftermentioned comparative example, K, L, M are suitable with this.But, the present invention wishes suppress its prosperity { 121}<111>orientation is by rolling and the rolling stable orientations that increases in common copper alloy.
On the other hand, in the present invention, it is distributed with { density of 110}<001>orientation crystal grain, the technique different from above-mentioned existing method is effective to control crystal orientation.Such as, following technique is effective, if but meet the crystalline state of regulation in the present invention, then manufacture method is not limited to following method.
One example of the manufacture method of the copper alloy plate of the present invention can enumerate following method: carries out melt-casting [operation 1] and obtains ingot bar, the hot-working [operation 3] such as heat treatment [operation 2], hot rolling that homogenize this ingot bar successively, water-cooled [operation 4], middle cold rolling [operation 5], the heat treatment [operation 6] for Precipitation, the most cold rolling [operation 7], stress relief annealing [operation 8].As long as cerium sulphate crystal and the physical property of regulation can be obtained, then can also omit stress relief annealing [operation 8].It should be noted that the present invention does not carry out solution heat treatment.That is, the operation after hot rolling does not carry out the heat treatment of more than 480 DEG C.
Or, another example of manufacture method as the copper alloy plate of the present invention, following method can be enumerated: carry out melt-casting [operation 1] and obtain ingot bar, this ingot bar is carried out successively middle cold rolling [operation 5], the heat treatment [operation 6] for Precipitation, the most cold rolling [operation 7], stress relief annealing [operation 8].In the case of Gai, the preferably moment at melt-casting [operation 1] carries out homogenizing and the adjustment of thickness of slab of composition in advance.In this operation, as long as cerium sulphate crystal and the physical property of regulation can be obtained, then can also omit stress relief annealing [operation 8].In the case of Gai, the present invention the most carry out solution heat treatment.That is, the operation after hot rolling does not carry out the heat treatment of more than 480 DEG C.
In order to control crystal orientation and the { density of 110}<001>orientation crystal grain of regulation in the present invention, realized by the combination of the specified conditions in the combination of a series of above-mentioned technique and following each operation, i.e., the condition making above-mentioned centre cold rolling [operation 5] is working modulus 20%～70%, making the condition of above-mentioned Ageing Treatment [operation 6] is at 300 DEG C～440 DEG C 5 minutes～10 hours, and to make the working modulus of above-mentioned the most cold rolling [operation 7] be more than 90%.This mechanism is presumed as follows.In above-mentioned Ageing Treatment [operation 6], the effect of (Ni, Co)-Si compound by separating out with the fine sizes of several below nm, distribution and the crystallization rotation of the indexing in the most cold rolling [operation 7] thereafter change.Additionally, by improving the rolling rate of the most cold rolling [operation 7], thus induce the division of the crystal grain in the most cold rolling [operation 7], make with fine state that { 110}<001>orientation crystal grain increases, and inhibits { 121}<111>crystallization that is orientated rotates and gathers simultaneously.
Herein, about the effect of precipitate, in existing Cu-(Ni, Co)-Si system, by making precipitate separate out with the size of about 10nm, thus precipitate self becomes the resistance of indexing, improves intensity.On the other hand, in the present invention, it is applied to orientation based on cold worked crystallization and the control of size, is very different in this.By the discovery of this new role and the new organizational controls that applies this discovery, it is possible to realize not obtained, high bendability is taken into account with high-yield strength characteristic in the past.
As the preferred heat treatment in each operation, the condition of processing, as described below.
About the heat treatment that homogenizes [operation 2], keep more than 1 hour, preferably 5 hours～10 hours at 960 DEG C～1040 DEG C.
About the hot-working such as hot rolling [operation 3], starting to the temperature range terminated to be 500 DEG C～1040 DEG C from hot-working, working modulus is 10%～90%.
About water-cooled [operation 4], usual rate of cooling is 1 DEG C/sec～200 DEG C/sec.
About middle cold rolling [operation 5], working modulus is 20%～70%.
Ageing Treatment [operation 6] is also referred to as Precipitation and processes, and its condition is to keep 5 minutes to 10 hours at 300 DEG C～440 DEG C, and preferred temperature range is 360 DEG C～410 DEG C.
The working modulus of the most cold rolling [operation 7] is more than 90%, is preferably more than 95%.The upper limit is not particularly limited, usually less than 99.999%.
About stress relief annealing [operation 8], keep 5 seconds～2 hours at 200 DEG C～430 DEG C.If the retention time is long, then intensity reduces, thus the short time annealing of preferably more than 5 seconds less than 5 minutes.
Herein, working modulus (or rolling rate) is by value defined in following formula.
Working modulus (%)={ (t1-t2)/t1}×100
In formula, t1Represent the thickness before rolling processing, t2Represent the thickness after rolling processing.
(physical property)
The copper alloy plate of the present invention preferably has following physical property.
(Vickers hardness: Hv)
Yield strength characteristic in the present invention carrys out quantification by Vickers hardness based on Vickers hardness test, and this Vickers hardness is the most proportional to yield strength, and the test film less than yield strength can be utilized to carry out quantification.
The Vickers hardness of the copper alloy plate of the present invention is preferably more than 280, more preferably more than 295, more preferably more than 310.The higher limit of the Vickers hardness of this sheet material is not particularly limited, if being additionally contemplates that Punching Technology etc., the most preferably less than 400.Vickers hardness in this specification refers to the value measured based on JISZ2244.Vickers hardness within the range in the case of, yield strength is also high level, in the case of the copper alloy plate of the present invention is used for adapter etc., can play the effect of the contact pressure that can substantially ensure that electric contact.
(yield strength: YS)
In a preferred implementation of the copper alloy plate of the present invention, rolling parallel direction is preferably more than 1020MPa, more preferably more than 1080MPa, more preferably more than 1140MPa with the meansigma methods of the yield strength (also referred to as yield stress or 0.2% yield point) of rolling vertical direction.The higher limit of the yield strength of this sheet material is not particularly limited, for example, below 1400MPa.
(electrical conductivity: EC)
Electrical conductivity is preferably more than 13%IACS, more preferably more than 15%IACS, more preferably more than 17%IACS, particularly preferably more than 19%IACS.About the upper limit of electrical conductivity, if more than 40%IACS, then intensity reduces sometimes.It is preferably below 40%IACS, more preferably below 34%IACS, more preferably below 31%IACS.
It should be noted that in the present invention, yield strength is value based on JISZ2241.It addition, above-mentioned " %IACS " represents the resistivity 1.7241 × 10 of international annealed copper standard (InternationalAnnealedCopperStandard)-8Ω m is set to electrical conductivity during 100%IACS.
(bendability: MBR/t)
About bendability, the minimum inner side bending radius (MBR:MinimumBendableRadius) not cracked during by bending machining is expressed as its standard relative to the ratio (MBR/t) of thickness of slab (t).In the copper alloy plate of the present invention, it is that 1020MPa is less than in the intensity band of 1160MPa in yield strength (YS), MBR/t is preferably less than 2, more preferably less than 1, it is that 1160MPa is less than in the intensity band of 1200MPa in yield strength (YS), MBR/t is preferably less than 3, more preferably less than 2, being 1200MPa less than in the intensity band of 1280MPa in yield strength (YS), MBR/t is preferably less than 4, more preferably less than 3.The lower limit of this MBR/t is not particularly limited, usually 0.
(thickness ranges of goods)
In an embodiment of the copper alloy plate (copper alloy bar) of the present invention, thickness is below 0.6mm, and in typical embodiment, thickness is 0.03mm～0.3mm.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to this.
(embodiment 1)
The raw material utilizing the high frequency smelting furnace alloy to being made up of Cu and inevitable impurity containing the alloying component element described in table 1 and remaining part melts, and casts it, obtains ingot bar.With the rolling rate described in following operation, through each rolling process, have adjusted the size of ingot bar, reach final thickness of slab (0.10mm) with noncontradictory.Further, utilize any one preparation method in following A, B, D and E, manufactured the test material of the copper alloy plate of the example according to the present invention and comparative example unlike this respectively.It should be noted that table 1 represents to employ which kind of preparation method in A, B, D and E.The thickness of final copper alloy plate is 0.10mm (100 μm).As long as not special declaration, then this final thickness of slab is the most identical in the case of preparation method J, K, L, M of the following stated.It should be noted that, table refers to be unsatisfactory in the present invention content of the alloying component of regulation, orientation density, { 110}<001>density [ρ] of crystal grain that is orientated or preparation method, or the preferred scope that physical property is unsatisfactory in the present invention with the numeral etc. represented by underscore.
(preparation method A)
For above-mentioned ingot bar, carry out keeping at 960 DEG C～1040 DEG C the heat treatment that homogenizes of more than 1 hour, directly carry out hot rolling with this condition of high temperature, until thickness of slab is 12mm, carry out water-cooled immediately.Further, after surface cut, the centre that rate is 20%～70% it is processed successively cold rolling, 300 DEG C～440 DEG C the most cold rolling, the stress relief annealings keeping 5 minutes～the Ageing Treatment of 10 hours, working modulus to be more than 90%.
(preparation method B)
Do not carry out homogenize heat treatment and the hot rolling of above-mentioned preparation method A, for above-mentioned ingot bar, after surface cut, it is processed the centre that rate is 20%～70% according to this cold rolling, 300 DEG C～440 DEG C cold rolling, the stress relief annealings keeping 5 minutes～the Ageing Treatment of 10 hours, working modulus to be more than 90%.
(preparation method D)
For above-mentioned ingot bar, carry out keeping at 960 DEG C～1040 DEG C the heat treatment that homogenizes of more than 1 hour, directly carry out hot rolling with this condition of high temperature, until thickness of slab is 12mm, carry out water-cooled immediately.Further, after surface cut, the centre that rate is 20%～70% it is processed successively cold rolling, in the most cold rolling, the stress relief annealing kept 5 minutes more than 500 DEG C and less than 700 DEG C～the Ageing Treatment of 10 hours, working modulus are more than 90%.
(preparation method E)
For above-mentioned ingot bar, carry out keeping at 960 DEG C～1040 DEG C the heat treatment that homogenizes of more than 1 hour, directly carry out hot rolling with this condition of high temperature, until thickness of slab is 12mm, carry out water-cooled immediately.Further, after surface cut, be processed successively the centre that rate is 20%～70% cold rolling, 300 DEG C～440 DEG C keep 5 minutes～the Ageing Treatment of 10 hours, working modulus be 80% less than 90% the most cold rolling, stress relief annealing.
The condition of the stress relief annealing in preparation method A, B, D and E is to keep 5 seconds～2 hours at 200 DEG C～430 DEG C.It should be noted that after each heat treatment or rolling, according to oxidation or the state of roughness of material surface, clean as desired by surface cut or acid or surface grinding removes the oxide layer on surface.It addition, according to shape, utilize tension leveler to correct when necessary.It addition, according to the concavo-convex transfer of Rolling roller or the difference of oil pit, in the case of the roughness of material surface is big, the rolling condition such as the drafts of 1 passage when adjusting mill speed, ROLLING OIL, the diameter of Rolling roller, the surface roughness of Rolling roller, rolling.
It addition, as other comparative examples, utilize any one in following preparation method J, K, L, M to manufacture experimently, obtain the test material of copper alloy plate.Preparation method J, the condition of K, L, M have followed the manufacture method described in each patent documentation, but the condition of solution heat treatment is different because of the addition element concentration in alloy, therefore, concentration Ni=3.81 mass % and Si=0.91 mass % of each composition in example 104 grade in the present embodiment are kept 1 minute as the condition being allowed to abundant solid solution, the condition employing of solution heat treatment at 900 DEG C.
(preparation method J) patent documentation 5: the preparation method described in embodiment that International Publication WO2011/068134A1
The raw material utilizing the DC method copper alloy composition to providing shown in table 1 below casts, and obtains thickness 30mm, width 100mm, the ingot bar of length 150mm.Then this ingot bar is heated to 950 DEG C, after this temperature keeps 1 hour, is rolled into thickness 14mm, carries out Slow cooling with the rate of cooling of 1K/ second, after reaching below 300 DEG C, carry out water-cooled.It follows that for two sides, carry out the surface cut of each 2mm respectively, after removing oxidation overlay film, implement rolling rate be 90%～95% cold rolling.Afterwards, carry out the intermediate annealing of 30 minutes at 350 DEG C～700 DEG C and carry out cold rolling with the cold rolling rate of 10%～30%.Afterwards, carry out the solution treatment of 1 minute at 900 DEG C, cool down with the rate of cooling of more than 15 DEG C/sec immediately.Then, implementing the Ageing Treatment of 2 hours under inert gas atmosphere in 400 DEG C～600 DEG C, carry out the finish rolling that rolling rate is less than 50% afterwards, making final thickness of slab is 100 μm.After finish rolling (the most cold rolling), implement the stress relief annealing of 30 seconds at 400 DEG C.
(preparation method K) patent documentation 6: the preparation method of the embodiment 3 described in Japanese Unexamined Patent Publication 2012-122114 publication
Utilize the low frequency smelting furnace of reducing atmosphere, after being melted down the raw material of the copper alloy composition provided shown in table 1 below is cast, produce the copper alloy ingot bar of the size of thickness 80mm, width 200mm, length 800mm, after this copper alloy ingot bar is heated to 900 DEG C～980 DEG C, hot rolling is utilized to make the hot rolled plate that thickness is 11mm, after this hot rolled plate water-cooled, two sides is carried out the surface cut of 0.5mm.Then, implement cold rolling with rolling rate 87%, after producing the cold-reduced sheet that thickness is 1.3mm, continuous annealing is implemented with the condition kept at 710 DEG C～750 DEG C 7 seconds～15 seconds, implement cold rolling (will carry out before solution treatment cold rolling) with working modulus 55%, produce the cold-reduced sheet of specific thickness.After this cold-reduced sheet is kept 1 minute at 900 DEG C, it is quenched, after implementing solution treatment, keeps 3 hours at 430 DEG C～470 DEG C, implement ageing and process.Then, carry out the mechanical lapping of granularity #600, after being implemented in the treatment fluid of the sulphuric acid of 5 mass % and the hydrogen peroxide of 10 mass % with the liquid temperature dipping pickling processes of 20 seconds of 50 DEG C, implement the most cold rolling of working modulus 15%, then implement continuous low temperature annealing with the condition kept at 300 DEG C～400 DEG C 20 seconds～60 seconds, produce copper alloy thin plate.
(preparation method L) patent documentation 7: the preparation method of embodiment 1 example No.1 described in Japanese Unexamined Patent Publication 2006-9108 publication
Utilize air furnace melting to provide the raw material of the copper alloy composition shown in table 1 below, be cast as the ingot bar of thickness 20mm × width 60mm.By this ingot bar after 1000 DEG C of homogenizing anneals implementing 3 hours, start hot rolling with this temperature.When thickness reaches 15,10 and 5mm, the material in rolling way is reheated 30 minutes with 1000 DEG C, after hot rolling, makes the thickness of slab of 3mm.Thereafter, carry out successively surface cut, thickness of slab cold rolling (working modulus 79%) to 0.625mm, with 900 DEG C of solution treatment keeping 1 minute, water-cooled, the thicknesss of slab cold rolling (working modulus 20%) to 0.5mm, keep the Ageing Treatment of 3 hours with 400 DEG C～600 DEG C.
(preparation method M) patent documentation 8: the embodiment described in Japanese Unexamined Patent Publication 2006-152392 publication, the preparation method of example 10
In air, the melting sources of the copper alloy composition shown in table 1 below will be provided under Linesless charcoal is coating in kryptol furnace, casting in the cast iron book mold (Block ッ Network モ Le De), obtain thickness be 50mm, width be 75mm, the ingot bar of a length of 180mm.Further, after the surface of ingot bar is carried out surface cut, it is hot-rolled down to till thickness reaches 15mm, the temperature of more than 750 DEG C be quenched in water with the temperature of 950 DEG C.Then, after removing removing oxide layer, the working modulus with 97% carries out cold rolling, uses salt bath furnace to carry out after 825 DEG C of heating solution treatment of 20 seconds, in water after quenching, by the cold-reduced sheet of final cold rolling formation 0.38mm that working modulus is 15%.Further, carry out keeping the Ageing Treatment of 4 hours at 420 DEG C.
For these examples according to the present invention and the test material of comparative example, measure as follows, have rated each characteristic.One it is listed in table 1 as a result.
A. density it is orientated
{ 111}, { 100}, { the incomplete pole graph of 110} is measured from material surface.With measure face specimen size as 25mm × mode of 25mm is measured.Based on 3 pole graphs measured, carry out ODF analysis.The symmetry of sample is orthotropic (Orthotropic) (being that minute surface is symmetrical at RD and TD), and launching number of times is 22 times.Further, { 121}<111>orientation, { 110}<001>orientation and { 001}<100>the orientation density that is orientated are obtained.
B.{110}<001>the density [ρ] of crystal grain that is orientated
Utilize FE-SEM/EBSD method to carry out the scanning of electron ray with 0.05 μm interval, measure, make crystal orientation figure.Herein, it is crystal boundary by the boundary definition that misorientation is more than 5 °.For each sample, carry out the mensuration of the field of view of size 50 μ m 50 μm in 3 visuals field respectively, obtain crystal orientation figure.About analysis, on obtained crystal orientation figure, extract out with ideal orientation the 110}<001>deviation angle that is orientated be ± 20 ° within crystal grain data, therefrom obtain the number of the crystal grain that major diameter is more than 0.2 μm.Further, by this number divided by all measuring area, as every 1 μm2There is the { 110}<001>density [ρ (individual/μm of crystal grain that is orientated2)]。
C. Vickers hardness [Hv]
According to JISZ2244, by material surface or through the cross-section determination Vickers hardness of mirror ultrafinish.Load is 100gf, obtains the meansigma methods of n=10.
D. yield strength [YS]
Any one in parallel direction (RD) or rolling vertical direction (TD) will be rolled as length direction, it is respectively cut out the test film of No. JISZ2201-13B from each test material, respectively 3 above-mentioned test films is measured according to JISZ2241.The percentage elongation measurement location utilizing contact is moved, and obtains load-deformation curve, reads 0.2% yield point.Further, by the yield strength of rolling parallel direction: YS (RD) and the yield strength of rolling vertical direction: the meansigma methods of YS (TD) is expressed as yield strength.
E. bendability [MBR/t]
Making bending direction is rolling parallel direction, and making bending axis is rolling vertical direction, is curved test (GoodWay bending).By above-mentioned each test material, obtained the strip test film of wide 1mm by compacting Punching Technology.Bent by above-mentioned GoodWay, carry out 90 ° of W bending machining according to JISZ2248, utilize the summit in observation by light microscope bending machining portion, investigated the presence or absence of crackle.About inner side bending radius, 6 levels being spaced with 0.1mm from 0.1mm to 0.6mm are tested, obtain the minimum bending radius (MBR) that can be curved processing, by representing bendability by standardized value MBR/t of thickness of slab (t) flawless.
F. electrical conductivity [EC]
For each test material, in the constant temperature mortise remaining 20 DEG C (± 0.5 DEG C), utilize four-terminal method to measure resistivity, calculate electrical conductivity.It should be noted that terminal pitch is from for 100mm.
[table 1]
Table 1
As shown in table 1, the example 101～108 of the regulation meeting the present invention is all that complete characteristic is excellent.The concentration of Ni/Co, Si is the highest in prescribed limit, then illustrate the highest yield strength YS.
On the other hand, in each comparative example, owing to alloy composition is unsatisfactory in the present invention condition of regulation, thus 110}<001>and be orientated orientation density, { at least one in the 110}<001>density [ρ] of crystal grain that is orientated is unsatisfactory in the present invention condition of regulation, and therefore Vickers hardness [Hv], yield strength [YS] both of which characteristic are poor.
In comparative example 151, Ni/Co, Si are very few, thus Vickers hardness [Hv] is low and then yield strength [YS] is poor.It addition, in the too much comparative example 152 of Ni/Co, Si, produce hot-rolled crackle, manufacturing is poor.Utilizing in the comparative example 153 of preparation method D, { 110}<001>the orientation density that is orientated is low and { 110}<001>density [ρ] of crystal grain that is orientated is low.In this comparative example 153, although electrical conductivity [EC] is high, but Vickers hardness [Hv] and yield strength [YS] are poor.Although additionally, yield strength [YS] is low, but bendability is poor compared with example of the present invention.In the comparative example 154 utilizing preparation method E, { 110}<001>the orientation density that is orientated is low and { 110}<001>density [ρ] of crystal grain that is orientated is low.In this comparative example 154, although electrical conductivity [EC] is high, but Vickers hardness [Hv] and yield strength [YS] are poor.Although additionally, yield strength [YS] is low, but bendability is poor compared with example of the present invention.
As other comparative examples, the comparative example 155 utilizing preparation method J, the comparative example 156 utilizing preparation method K, the comparative example 157 that utilizes preparation method L are all that { 110}<001>density [ρ] of crystal grain that is orientated is low.Although these comparative examples 155,156,157 electrical conductivity [EC] are high, but Vickers hardness [Hv] and yield strength [YS] are poor.Wherein, in comparative example 155, { 110}<001>the orientation density that is orientated is the most too small, and { 001}<100>the orientation density that is orientated is big.
Utilizing in the comparative example 158 of preparation method M, according to the record of patent documentation 8, { 001}<100>orientation gathers consumingly, but in the supplementary test, trial-production of the present inventor, and { 001}<100>the orientation density that is orientated is 2, and the area occupation ratio that measures based on EBSD is the lowest is 2%.It addition, { 110}<001>density [ρ] of crystal grain that is orientated is low, and electrical conductivity [EC] is though height, but Vickers hardness [Hv] and yield strength [YS] are poor.It addition, in comparative example 158, { 110}<001>the orientation density that is orientated also shows that too small result.
(embodiment 2)
Utilize manufacture method same as in Example 1 and test/assay method, use each Albatra metal shown in table 2 to manufacture copper alloy plate, evaluate its characteristic.Result is listed in table 2.
[table 2]
As shown in table 2, the example 201～208 of the regulation meeting the present invention is all that complete characteristic is excellent.Additive effect by secondary addition element, although be not in total Test example, but confirm { the tendency that the 110}<001>density [ρ] of crystal grain that is orientated becomes big, Vickers hardness [Hv] and yield strength [YS] improves.
The macrograph of example 204 shown in Fig. 4.This is the magnified partial view being measured the crystal boundary figure obtained by FE-SEM/EBSD, and only { 110}<001>orientation crystal grain white illustrates.
On the other hand, in each comparative example, owing to alloy composition is unsatisfactory in the present invention condition of regulation, thus 110}<001>and be orientated orientation density, at least one in the 110}<001>density [ρ] of crystal grain that is orientated is unsatisfactory in the present invention condition of regulation, and therefore Vickers hardness [Hv], yield strength [YS] both of which characteristic poor.
In comparative example 251, secondary addition element is too much, and manufacturing is poor.Utilizing in the comparative example 252 of preparation method D, { 110}<001>the orientation density that is orientated is low and { 110}<001>density [ρ] of crystal grain that is orientated is low.In this comparative example 252, although electrical conductivity [EC] is high, but Vickers hardness [Hv] and yield strength [YS] are poor.And then, although yield strength [YS] is low, but bendability is poor compared with example of the present invention.Utilize in the comparative example 253 of preparation method E, obtained the result as comparative example 252.
As other comparative examples, the comparative example 254 utilizing preparation method J, the comparative example 255 utilizing preparation method K, the comparative example 256 that utilizes preparation method L are all that { 110}<001>density [ρ] of crystal grain that is orientated is low.Although these comparative examples 254,255,256 electrical conductivity [EC] are high, but Vickers hardness [Hv] and yield strength [YS] are poor.Wherein, in comparative example 254, { 110}<001>the orientation density that is orientated is the most too small, and { 001}<100>the orientation density that is orientated is big.
Utilizing in the comparative example 257 of preparation method M, according to the record of patent documentation 8, { 001}<100>orientation gathers consumingly, but in the supplementary test, trial-production of the present inventor, and { 001}<100>the orientation density that is orientated is 2, and the area occupation ratio that measures based on EBSD is the lowest is 2%.It addition, { 110}<001>density [ρ] of crystal grain that is orientated is low, and electrical conductivity [EC] is though height, but Vickers hardness [Hv] and yield strength [YS] are poor.It addition, in comparative example 257, { 110}<001>the orientation density that is orientated also shows that too small result.
The macrograph of comparative example 252 shown in Fig. 5.This is the magnified partial view being measured the crystal boundary figure obtained by FE-SEM/EBSD, and only { 110}<001>orientation crystal grain white illustrates.
It addition, as other comparative examples, utilize following preparation method N to manufacture experimently, obtain the test material of copper alloy plate.
Embodiment 1 described in (preparation method N) Japanese Unexamined Patent Publication 2009-074125
For forming the acid bronze alloy of melt-casting with Cu-2.3Ni-0.45Si-0.13Mg (being quality %), utilize copper mold to carry out semi-continuous casting, cast out the square-section ingot bar of sectional dimension 180mm × 450mm, length 4000mm.Then, it is heated to 900 DEG C, is 22% to carry out hot rolling with the 1 average working modulus of passage, makes thickness 12mm, begin to cool down from 650 DEG C, carry out water-cooled with the rate of cooling of about 100 DEG C/min.After two sides carries out the surface cut of 0.5mm respectively, to make thickness be 2.5mm (working modulus=77.3%) by cold rolling, and the temperature with 500 DEG C carries out the Ageing Treatment of 3 hours in an ar atmosphere.And then carry out cold rolling, making thickness is 0.3mm (working modulus=88.0%), carry out the annealing of 1 minute in an ar atmosphere in 500 DEG C, to make thickness be 0.15mm (working modulus=50.0%) by the most cold rolling, carries out the stress relief annealing of 1 minute in an ar atmosphere in 450 DEG C.
For the test material of this comparative example, measure as described above, evaluate each characteristic.One it is listed in table 3 as a result.
In the comparative example 258 utilizing preparation method N, and 121}<111>be orientated orientation density, { 110}<001>the orientation density that is orientated and { density of 110}<001>orientation crystal grain is unsatisfactory for the scope of the present invention, and Vickers hardness [Hv], yield strength [YS] are poor.
Effectiveness of the invention is confirmed by above-described embodiment.

Claims (10)

1. a copper alloy plate, it is characterized in that, it has a following composition: containing any a kind or 2 kinds and 0.40 mass % in Ni and Co adding up to 1.80 mass %～8.00 mass %～the Si of 2.00 mass %, and remaining part is made up of copper and inevitable impurity
121}<111>the orientation density that is orientated is less than 6,110}<001>the orientation density that is orientated is more than 4,
Have that { 110}<001>density of crystal grain that is orientated is 0.40/μm2Above.
2. a copper alloy plate, it is characterized in that, it has a following composition: containing any a kind or 2 kinds, 0.40 mass %～the Si of 2.00 mass % in Ni and Co adding up to 1.80 mass %～8.00 mass % and add up to 0.000 mass %～2.000 mass % the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti to form at least one element, and remaining part is made up of copper and inevitable impurity
121}<111>the orientation density that is orientated is less than 6,110}<001>the orientation density that is orientated is more than 4,
Have that { 110}<001>density of crystal grain that is orientated is 0.40/μm2Above.
3. copper alloy plate as claimed in claim 2, it contains at least one element in the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition adding up to 0.005 mass %～2.000 mass %.
4. the copper alloy plate as according to any one of claims 1 to 3, its Vickers hardness is more than 280.
5. an adapter, its copper alloy plate comprised according to any one of Claims 1 to 4 forms.
6. the manufacture method of a copper alloy plate, it is characterised in that this manufacture method carries out following operation successively:
Melt-casting operation, wherein, to there is the melting sources of following composition and cast, this consists of: containing any a kind or 2 kinds and 0.40 mass % added up in Ni and Co of 1.80 mass %～8.00 mass %～the Si of 2.00 mass %, and remaining part is made up of copper and inevitable impurity；
Working modulus is the middle cold rolling process of 20%～70%；
Ageing treatment process, wherein, carries out 5 minutes～10 hours heat treatments at 300 DEG C～440 DEG C；With
Working modulus is the final cold rolling process of more than 90%.
7. the manufacture method of a copper alloy plate, it is characterised in that this manufacture method carries out following operation successively:
Melt-casting operation, wherein, to there is the melting sources of following composition and cast, this consists of: at least one element in group containing any a kind or 2 kinds, 0.40 mass %～the Si of 2.00 mass % in Ni and Co adding up to 1.80 mass %～8.00 mass % and choosing free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition adding up to 0.000 mass %～2.000 mass %, and remaining part is made up of copper and inevitable impurity；
Working modulus is the middle cold rolling process of 20%～70%；
Ageing treatment process, wherein, carries out 5 minutes～10 hours heat treatments at 300 DEG C～440 DEG C；With
Working modulus is the final cold rolling process of more than 90%.
8. the manufacture method of copper alloy plate as claimed in claim 7, it contains at least one element in the group selecting free Sn, Zn, Ag, Mn, P, Mg, Cr, Zr, Fe and Ti composition adding up to 0.005 mass %～2.000 mass %.
9. the manufacture method of the copper alloy plate as according to any one of claim 6～8, wherein, between described melt-casting operation and described middle cold rolling process, carries out following operation successively:
Homogenize heat treatment step, wherein, carries out the heat treatment of more than 1 hour at 960 DEG C～1040 DEG C；With
From hot-working start to the temperature range terminated be 500 DEG C～1040 DEG C, working modulus be the hot procedure of 10%～90%,
Operation after described hot-working does not carry out the heat treatment of more than 480 DEG C.
10. the manufacture method of the copper alloy plate as according to any one of claim 6～9, wherein, carries out keeping 5 seconds～the stress relief annealing of 2 hours at 200 DEG C～430 DEG C after described final cold rolling process.
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